Preparation of Heat Resistant Oxide Coatings by the Sol-Gel Process and Their Application to Surface Modification of Metal Sheets

溶胶-凝胶工艺是从金属烷氧化物开始的，是制备涂层的一种混合工艺。本研究项目旨在开发溶胶-凝胶工艺，用于在金属基材上涂覆氧化膜，从而改变其表面性能。得到了以下结果：将甲基加入到SiO_2涂层中，可以弯曲和压制金属基材，而不会破坏涂层。用铬酸和硫酸溶液对基体进行预处理，由于氧化层的形成，提高了SiO_2涂层在金属表面的附着力。以辛酸锆为原料，在金属板上连续涂覆ZrO_2薄膜。此外，在ZrO_2膜中掺入氟，使ZrO_2膜具有良好的拒水性。高度可水解的金属烷氧化合物，如al -烷氧化合物，用-二酮和胺稳定。稳定剂的作用很大程度上依赖于溶剂。以乙酰丙酮稳定的钛、锆烷氧化物为原料，在常压气氛下制备了PbTiO_3 -pbzro_3铁电薄膜。考察了MO-B<@D22@>D2O<@D23@>D2- sio <@D22@>D2 （M=Mg, Zn）和P<@D22@ b> D2O<@D25@>D2- b <@D22@>D2O<@23@>D2- sio <@D22@>D2体系钝化膜的制备条件。在TiO<@D22@>D2- sio <@D22@>D2体系中的薄膜也被发现具有良好的玻璃基板耐候性。在TiO_2-SiO_2溶胶中加入有机聚合物延缓了凝胶化，并使凝胶膜上的精细图案化成为可能。这一发现可应用于玻璃基板上预凹槽的形成。以Li、Ti烷氧化物和磷酸为原料，在较低温度下制备了离子导电化合物LiTi_2(PO_4)_3。含有H_3PMO_<12>O_<40>的SiO_2薄膜也表现出较高的质子传导率。

The sol-gel process, which starts from metal-alkoxides, is one of the pomising processes for the preparation of coating films. This research project was carried out to develop the sol-gel process for the coating of oxide films on metal substrates and thereby to modify the properties of their surfaces. The following results were obtained.1. The incorporation of methyl groups into SiO_2 coatings enabled to bend and press metal substrates without pealing of the coatings. The pre-treatment of the substrates with a solution of chromic acid and sulfuric acid improved the adhesion of SiO_2 coatings on the metal surfaces due to the formation of oxide layers.2. ZrO_2 films were continuously coated on metal sheets using zirconium octylates as starting materials. Moreover, the incorporation of fluorine into ZrO_2 films brought about the good water repellency.3. Highly hydrolyzable metal alkoxides, such as Al-alkoxides, were stabilized with beta-diketones and amines. The effects of stabilizer were however found to be greatly dependent on solvents.4. PbTiO_3 -pbzro_3 ferroelectric films were prepared in an ambient atmosphere from alkoxides of Ti and Zr stabilized with acetylacetone.5. Preparation conditions of passivation films in the MO-B<@D22@>D2O<@D23@>D2-SiO<@D22@>D2 (M=Mg, Zn) and P<@D22@>D2O<@D25@>D2-B<@D22@>D2O<@23@>D2-SiO<@D22@>D2 systems were examined. The films in the TiO<@D22@>D2-SiO<@D22@>D2 system were also found to have good weathering-resistance for glass substrates.6. The addition of organic polymers to TiO_2-SiO_2 sols retarded the gelation and gave the gel films on which fine-patterning was possible with a stamper. This finding can be applied to the formation of pregrooves on glass substrates.7. Ionic-conducting compound LiTi_2(PO_4)_3 was prepared at relatively low temperatures from alkoxides of Li and Ti and phosphoric acid. SiO_2 films containing H_3PMO_<12>O_<40> were also found to show a high proton-conduction.